Preparing permanent press garments by treating with composition therefor

ABSTRACT

A fabric having been impregnated with a composition comprising a neoprene elastomer, a polyisocyanate, polyisothiocyanate, blocked derivatives and mixtures thereof, and a metal oxide are found to have a propensity for subsequent durable dry setting in a preselected configuration. Fabrics which have been prepared and set in this manner exhibit improved crease retention, flat dry stability and resistance to shrinkage even when subjected to home laundering operation.

United States Patent [151 3,640,675

Thomas 1 Feb. 8, 1972 [54] PREPARING PERMANENT PRESS FOREIGN PATENTS ORAPPLICATIONS GARMENTS BY TREATING WITH COMPOSITION THEREFOR Manuel A.Thomas, 716 Palmetto St., Spartanburg, SC. 29302 Filed: Feb. 19, 1968Appl. No.: 706,605

Inventor:

US. Cl ..8/1 15.6, 8/1 15.7, 8/116.2, 8/127.6,1l7/139.5 R, 117/163,117/141, 117/161 UC, 117/161 UD, 1l7/139.4, 8/DIG.11, 38/144 Int. Cl..D06m 15/28, D06m 15/50 Field oISearch ..8/l16.2,115.6,115.7;117/139.5, DIG. 7

References Cited UNITED STATES PATENTS Herndon 1 54/ 136 OTHERPUBLICATIONS Great Britain France Catton The neorenes, 1953, p. 5

Primary Examiner-Donald Levy Assistant ExaminerPatricia C, IvesAtt0rney-Norman C. Armitage and H. William Petry [57] ABSTRACT 10Claims, No Drawings PREPARING PERMANENT PRESS GARMENTS BY TREATING WITHCOMPOSITION THEREFOR BACKGROUND OF THE INVENTION This invention relatesto a process for improving characteristics of textile fibers, and moreparticularly, to the preparation of fabrics having a propensity forsubsequent durable dry setting.

Garments containing creases which are durable to home launderingoperations are known in the art. Garments prepared from cellulosicfiber-containing fabrics having home laundry durable creases set thereinhave recently found wide acceptance in the industry. Cellulosic garmentsof the abovementioned types and the methods for their preparation areset forth in US. Pat. No. 2,974,432. Satisfactory processes for thepreparation of durable creases in wool fabrics which will stand homelaundering operations also have been known, but these processesgenerally involve some form of wet chemical treatment at the time ofsetting. For example, one type of wool fabric known to be useful in thepreparation of garments having creases durable to home launderingoperations is subjected to certain chemical and physical treatments infabric form, cut and formed into a garment, and thereafter subjected toadditional chemical treatments prior to setting. Such a procedurerequires that the cutter and garment manufacturer maintain skilledpersonnel and special equipment for the treatment of these fabrics priorto setting. For these reasons, such methods for preparing permanentpress wool fabrics have not been completely accepted in the industry.

Another method for preparing durable creases in natural fiber-containingfabrics has involved the use of blends of thermoplastic fibers andnatural fibers such as cotton and wool. By setting the thermoplasticcomponent of the fabric at temperatures near the melting point of thethermoplastic fiber, a crease is produced which has a certain degree ofdurability to home laundering operations. However, the setting operationgenerally destroys the desirable hand and surface effects of thefabrics.

Still another method involves a three-blend fabric containing forexample, 50 percent wool, 40 percent rayon, and percent nylon herein therayon component is reacted with a typical postcured resin such asdihydroxy dimethyl ethylene urea and subsequently pressed and cured inan oven.

SUMMARY OF THE INVENTION These problems have been overcome by providingtextile fabrics having a propensity for subsequent durable setting whichhave been impregnated with a composition comprising a neopreneelastomer, a compound selected from the class consisting ofpolyisocyanates; polyisothiocyanates, blocked derivatives and mixturesthereof, and a metal oxide. These impregnated fabrics may then be cut,converted into a garment, maintained in a desired configuration, andthereafter subjected to a temperature sufficient to cure the impregnatedfabric. The curing is a dry curing process thereby eliminating anynecessity for the cutter and garment manufacturer to further treat thegarment before it is pressed in its permanent configuration.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The textile fabrics which areuseful in this invention may be prepared from virtually all types offibers ranging from fabrics containing 100 percent natural fibers suchas cotton or wool to fabrics composed exclusively of synthetic fiberssuch as polyesters and polyamides. Blends of these fibers also have beenvaluable for preparing garments having durable creases. Further examplesof fabrics include those containing natural fibers such as flax, ramie,alpaca, vicuna, mohair, cashmere, guanaco, camel hair, llama, fur, suedeand silk. Synthetic fibers include polyamides such as polyhexamethyleneadipamide; polyesters such as polyethylene terephthalate; acrylic fiberssuch as polyacrylonitrile, homopolymers or copolymers of acrylonitrile,such as acrylonitrile/methylacrylate (85:15);

and cellulosic derivatives such as cellulose acetate and viscose rayon.The invention is particularly adapted to wool fabrics which heretoforehave been particularly difficult to set by post curing in a preselectedconfiguration durable to home laundering.

Examples of fabrics wherein synthetic fibers are blended with naturalfibers include wool/nylon (:15); Acrilan/wool (55:45); Orlon/wool(65:35); Dacron/wool (55:45); wool/rayon (65:35); and wool/rayon/nylon(65:25:10).

Laminated fabrics are also susceptible to improvement by this invention.The laminated fabrics can be composed of two or more layers of fabricbonded together with an adhesive. Such laminated fabrics are well knownin the art. The outer layer is generally a woven or knitted fabriccomprised of natural fibers, synthetic fibers or blends thereof.Examples of such fibers and fabrics have been listed above. The inner orbacking layer of the laminated fabric is preferably a knitted fabricobtained from spun or continuous filament yarns. Particularly useful andpopular knitted fabrics include those prepared from such fibers ascotton, nylon, polyester, cellulose acetate, rayon and viscose rayon.Knitted tricot fabrics such as acetate and nylon tricot have achievedwide popularity.

The neoprenes useful in the composition of this invention arechloroprene based synthetic elastomers. These may be either polymers ofchloroprene or copolymers of chloroprene with other polymerizableethylenically unsaturated compounds, such as acrylonitrile.Copolymerization is generally catalyzed by a potassium persulfatecatalyst. The progress of the polymerization is followed by means ofspecific gravity changes. Depending upon the type of neoprene latexdesired, a shortstop may be added after the desired conversion has beenobtained, or the polymerization may be carried to completion.

In this manner, a wide variety of neoprenes can be prepared. Examples ofsolid neoprenes which are available commercially include thesulfur-modified" types, such as Neoprene Type ON (a sulfur-modifiedchloroprene polymer stabilized by a thiuram disulfide), Neoprene TypeGN-A (a sulfur-modified chloroprene polymer stabilized by a thiuramdisulfide and containing a secondary aromatic amine stabilizer),Neoprene Type GRT (a sulfur-modified chloroprene polymer stabilized by athiuram disulfide and containing a nondiscoloring antioxidant), andNeoprene Type W, (a nonsulfur-modified general-purpose type ofneoprene). Although both the GN and W Types are made by emulsionpolymerization chloroprene, the W type of neoprene has a more uniformmolecular structure and does not contain sulfur or other compoundscapable of decomposing to yield free sulfur. As a result of thesedifferences, Type W neoprene displays improved storage ability andbetter processing properties. Magnesia and zinc oxide are requiredmodifying agents in all neoprene Type W formulations.

Neoprene Type Q is a copolymer of chloroprene and acrylonitrilestabilized with a thiuram disulfide and containing a nondiscoloringantioxidant. These and other neoprenes are described in more detail inthe book entitled The Neoprenes, Principals of Compounding andProcessing by Neil L. Catton, published in 1953 by E. I. duPont deNemours and Co., Wilmington, Del.

Neoprene latices are extremely useful in the preparation of thecompositions of this invention, especially in the preparation of aqueousdispersions or emulsions of the compositions. The neoprene latices areemulsions of polymerized chloroprene or copolymers of chloroprene inwater, which contain emulsifying agents and stabilizers. The latices aremilklike liquids containing from about 35 to 60 percent total solids.These latices are further characterized in that they do not tend tosettle out significantly, even though the neoprene polymer has aspecific gravity considerably higher than that of the liquid in which itis suspended. The different types of neoprene latices currentlyavailable are obtained by varying certain manufacturing proceduresincluding the emulsification, catalyst and modifier systems. Resultinglatices differ from one another in polymer and colloidal properties. Avariety of neoprene latices are available from the E. I. duPont deNemours and Co. and several of these are described in the book entitledNeoprene Latex, Principals of Compounding and Processing, by John C.Carl, 1962. Examples of such neoprene latices include Neoprene Latex 400(a high modulus and ozone resistant latex containing about 50 percentsolids having a Brookfield viscosity of 15 c.p.s.), Neoprene Latex 750(a low-modulus latex which is highly resistant to crystallization;contains about 50 percent solids and has a Brookfield viscosity of 13c.p.s.), Neoprene Latex 650 is a concentrated form of Latex 750containing about 60 percent solids and having a Brookfield viscosity of4,000 c.p.s. An example of a latex emulsion containing a copolymer ofchloroprene and acrylonitrile is Neoprene Latex 450. The copolymer ishighly oil resistant and noncrystallizing.

The particular solid neoprene or neoprene latex chosen for thepreparation for the compositions of the invention will depend upon therelationship of the properties of the neoprene and those desired of thefabrics treated with the composition. This selection will be apparent tothose skilled in the art.

The compositions of this invention also contain a compound selected fromthe class consisting of polyisocyanates, polyisothiocyanates, blockedderivatives or mixturesthereof. Polyisocyanates and blockedpolyisocyanates are preferred.

The suitable isocyanates that are useful in accordance with thisinvention include, for example, aryldiisocyanates, such as 2,4-toluenediisocyanate, 2,6-toluene diisocyanate, 4,4- diphenylmethanediisocyanate, p-phenylene diisocyanate, 1,5- naphthylene diisocyanate,m-phenylene diisocyanate, diphenyl-4,4'-diisocyanate,l-isopropylbenzene-3,S-diisocyanate, lmethyl-phenylene-2,4-diisocyanate,naphthylene-l,4-diisocyanate, diphenyl-4,4'-diisocyanate, S-nitro-l,3-phenylene diisocyanate, xylylene-l 4-diisocyanate,xylylene-l,3-diisocyanate, 4,4'-diphenylenemethane diisocyanate,4,4-diphenylenepropane and diisocyanate; alkylene diisocyanates such astetramethylene diisocyanate and hexamethylene diisocyanate; as well asmixtures thereof and including the equivalent isothiocyanates. Of thesecompounds, the aryldiisocyanates are preferred because of theirsolubility and availability.

Additional isocyanates include polymethylene diisocyanates anddiisothiocyanates, such as ethylene diisocyanate, dimethylenediisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate,tetramethylene diisocyanate, pentamethylene diisocyanate, and thecorresponding diisothiocyanates; alkylene diisocyanates anddiisothiocyanates such as propylene-l,2-diisocyanate,2,3-dimethyltetramethylene diisocyanate and diisothiocyanate,butylenel,2-diisocyanate, butylene-l ,3-diisothiocyanate, anddiisothiocyanates such as ethylidene diisocyanate (CH CH(N- CO) andheptylidene diisothiocyanate (CH (CH CH(CNS) cycloalkylene diisocyanatesand diisothiocyanates such as 1,4-diisocyanatacyclohexane,cyclopentylenel ,3-diisocyanate, and cyclohexylenel ,2-diisothiocyanate;aromatic polyisocyanates and polyisothiocyanates such as phenylethylenediisocyanate (C .,l-l CH(NCO)CH NCO); diisocyanates anddiisothiocyanates containing heteroatoms such as SCNCH OCH NCS, andSC(H)(CH S(CH NCS l,2,3,4-tetraisocyanatobutane, butane-l ,2,2-triisocyanate, toluylene-2,4,6-triisocyanate, toluyene-2,3,4-triisocyanate, benzene-1 ,3,5-triisocyanate, benzene-1 ,2,3-triisocyanate, l-isocyanate-4-isothiocyanatohexane, and 2- chloro-l,3-diisocyanatopropane.

The isocyanates or isothiocyanates may be derived from the correspondingblocked compound in accordance with conventional technology. Blockedisocyanates contain little or no free isocyanate groups as the result ofthe additon onto these groups by active hydrogen compounds (asdetermined by the Zerewitinoff method). These addition products arerelatively inert at room temperatures but have only limited thermalstability. Thus upon heating beyond a certain temperature, called thedissociation temperature, the addition product is activated, or freedand takes part in the curing process.

In the preparation of the adducts, the polyisocyanate and the adductforming compound are usually dissolved in a suitable inert solvent suchas toluene, methyl ethyl ketone, or odichlorobenzene. The solutions arestirred together and permitted to stand. The reaction should be causedto take place at a temperature below the decomposition temperature ofthe desired product and preferably at a temperature not exceedingapproximately C. In most instances, the reaction will proceedsatisfactorily at room temperature. When the solvent used for theisocyanate compound and blocking agent is not also a solvent for theadduct formed, the adduct formed separates from the solution and isremoved therefrom by filtration or evaporation of the solvent. The timerequired for the adduct to form will vary from a few minutes to severalhours depending upon the particular reactants used. The precipitatedproduct will probably contain small amounts of unreacted material which,if necessary, can be removed by recrystallization or extractionprocedures known to those skilled in the art.

Preferred adduct-forming compounds produce adducts which may beactivated, or unblocked, by heat alone. Typical active hydrogencompounds which provide heat-reversible adducts include the following:

1. Tertiary alcohols, such as tertiary butyl alcohol, tertiary amylalcohol, dimethyl ethinyl carbinol, dimethyl phenyl carbinol, methyldiphenyl carbinol, triphenyl carbinol, l-nitro tertiary butyl carbinol,and l-chloro tertiary butyl carbinol;

2. Secondary aromatic amines which contain only one group having ahydrogen reactive with an isocyanate group, such as the diarylcompounds, including diphenyl amine, oditolyl amine, m-ditolyl amine,p-ditolyl amine, N-phenyl toluidine, N-phenyl xylidine, phenyl alphanaphthyl amine, phenyl beta naphthyl amine, carbozole, and the nuclearsubstituted aromatic compounds such as 2,2-dinitro diphenyl amine and2,2'-dichloro diphenyl amine;

3. Mercaptans, such as Z-mercaptobenzothiazole, 2-mercapto thiazoline,dodecyl mercaptan, ethyl 2-mercapto thiazole, dimethyl Z-mercaptothiazole, beta naphthyl mercaptan, alpha naphthyl mercaptan, phenylZ-mercapto thiazole, 2- mercapto 5-chloro-benzothiazole, methylmercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, andethinyl dimethyl thicarbinol;

4. Lactams, such as epsilon-caprolactam, deltra-valerolactam,gamma-butyrolactam, and beta-propiolactam;

5. lmides, such as carbimide, succinimide, phthalimide, naphthalimide,and glutarimide;

6. Monohydric phenols in which the hydroxyl group is the only groupcontaining hydrogen reactive with the isocyanate group, such as thephenols, cresols, xylenols, trimethyl phenols, ethyl phenols, propylphenols, chloro phenols, nitro phenols, thymols, mono alpha phenyl ethylphenol, di alpha phenyl ethyl phenol, tri alpha phenyl ethyl phenol andtertiary butyl phenol;

7. Compounds containing enolizable hydrogen, such as acetoacetic esters,diethyl malonate, ethyl n-butyl malonate, ethyl benzyl malonate, acetylacetone, acetonyl acetone and benzimidazole.

The adduct-forming compounds, should, of course, possess only one groupcontaining a reactive hydrogen atom. The presence of more than one suchgroup would permit polymerization reactions with the polyisocyanatewhich are not desired in most instances. Among the more preferableadduct-forming compounds are included diphenyl amine and phenol.

The use of such blocked polyisocyanates is preferred in his inventionfor a number of reasons which are based on the fact that the blockedisocyanates are not reactive under normal conditions. The selection ofsuch blocked isocyanates permits the use of water as the dispersingmedium and avoids the necessity of utilizing organic solvents. Moreover,the use of blocked isocyanates permits the preparation of stablecompositions regardless of the solvent and enables one to preparefabrics having a propensity for subsequent durable setting severalmonths after treatment without any further chemical treatment. Forexample, as further illustrated elsewhere in this application, a fabriccan be converted into a garment and set in a given configuration by dryheating and pressing months after the fabric has been impregnated withthe compositions of this invention containing a blocked polyisocyanate.Of course, the heating and pressing temperatures must be above thedissociation temperature of the blocked isocyanate.

'A third essential ingredient in the compositions of the invention is ametal oxide such as zinc oxide, magnesium oxide e.g., magnesia),litharge red lead (lead tetraoxide), calcium oxide, iron oxide andtitanium dioxide. The metal oxides perform three important functions inthe compositions of the invention. They promote cross-linking or curingof the composition; they improve resistance to aging, heat, light andweather; and they further act as acid acceptors. The preferred metaloxide is zinc oxide although a combination of magnesium and zinc oxideis desirable and virtually necessary in compositions containing certainneoprenes, such as, for example, Neoprene-Type GN.

Generally, about 5 parts of metal oxide per 100 parts of neopreneprovide satisfactory results although greater or smaller amounts mayalso be utilized. For example, in some instances, as much as parts ofthe metal oxide may be incorporated, and higher amounts, from 10 toparts, are often recommended in stocks requiring maximum heat resistancealthough the use of such large quantities results in products havingsomewhat reduced storage stability. Less than 5 parts per 100 issometimes used in transparent products in order to reduce the pigmentingeffect although such products should not be used in intimate contactwith acid sensitive materials.

It is possible in some instances to obtain a significant amount ofcuring in the absence of a metal oxide if a zinc-containing acceleratoris used. Examples of such accelerators include the zinc salt of2-mercaptobenzothiazole or zinc dibutyl dithiocarbamate. Productsutilizing these accelerators should, however, be used with caution sincetheir aging resistance will be below that obtained from the metaloxides.

Although the compositions comprising a neoprene elastomer, a metaloxide, and a polyisocyanate or polyisothiocyanate may be applied asprepared to a fabric, it is often desirable that the composition bediluted with a liquid which is relatively inert to the compositions.That is, the compositions should be either prepared or added to a liquidto form solutions, dispersions or emulsions of the composition. Theamount of liquid is not critical except that the viscosity of thesolution, dispersion or emulsion should be sufficiently low to permitthe solution to impregnate the fabric. Maximum benefit is obtained whenthe composition of the invention impregnates the fabric as opposed tothe deposition of a coating on the fibers of the fabric. For thisreason, Brookfield viscosities of less than 5,000 centipoises aredesirable and preferred.

The liquid utilized in the preparation of the solutions, dispersions, oremulsions of the invention may be either nonreactive organic solvents orin some instances, as explained further below, water. By nonreactive"solvents as used herein is meant a solvent in which reactivity betweenthe isocyanate and the neoprene or the fabric, even in the presence of acatalyst, is substantially inhibited.

Suitable organic solvents include halogenated hydrocarbons, such astrichloroethylene, methylene chloride, perchloroethylene, ethylenedichloride, and chloroform; aromatic solvents such as toluene, xylene,benzene and mixed aromatics such as the Solveseso types, n-butylacetate, p-dioxane and methyl isobutyl ketone. Mixtures of such solventsmay also be used.

The use of a nonreactive organic liquid permits the combination of allof the desired components of the composition in a single solution,emulsion or dispersion without any sub stantial reaction occurring amongthe components. In this manner, all of the components, including thecure accelerators are impregnated uniformly in the fabric incontrollable amounts.

The use of water as a diluent or dispersing agent for the compositionsof the invention is limited to those compositions wherein the isocyanateor isothiocyanate has been prereacted with one of the adduct-formingcompounds described previously to form a blocked isocyanate or blockedpolyisothiocyanate. Blocking of the reactive isocyanate groups isessential since these groups react readily with water if not blockedthereby eliminating their utility in the aqueous compositions of theinvention. As mentioned previously, the compositions of this inventionwhich contain the blocked isocyanates or isothiocyanates provideespecially desirable results since these compositions may be impregnatedinto the fabric and dried without substantial reaction among thecomponents of the composition and the fabric substrate. Reaction onlyoccurs when the impregnated fabric is heated to a temperature which issufficient to unblock or dissociate the blocked isocyanate which is thenfree to react. Until the impregnated fabric is heated to such atemperature, the fabric is in a presensitized state having a propensityfor subsequent permanent pressing. The fabric presensitized in thismanner is further characterized by excellent stability and shelf life,and the ability to be set in a given configuration in the dry state byheat alone. That is, the fabric need not be wet by water or any otherliquid or reactant to develop the desirable permanent presscharacteristics.

Although the compositions described above are, in themselves, useful,they nevertheless are susceptible to improvement by the incorporation ofother additives which impart properties desired for special applicationsand needs. Such additives include antioxidants, acrylic resins,polyhydroxy com pounds, alkyd resins, therrnosetting resins such asphenolic resins, melamine resins and urea formaldehyde resins,formaldehyde donors, silicones and wetting agents. The type, number andamount of these optional additives included in the compositions of theinvention will depend upon the particular properties desired.

Neoprene-containing compositions have been found to age in the presenceof air due to the slow attact by oxygen. Such aging results in areduction of the desirable physical properties. This process iscatalyzed further by heat and sunlight. Therefore, the use of efficientantioxidants is desirable if not essential in neoprene-containingcompositions in order to assure outstanding resistance to aging. Theantioxidants should be selected with care since they are not equallyeffective as antioxidants, and some have some undesirable secondaryeffects such as increased discoloration upon exposure to light orstaining of the finishes. The more efiective antioxidants generallycause discoloration or staining. The most commonly used antioxidants forblack or dark-colored stocks are the amine-type antioxidants such asthose available under the trade name Neozone". Neozone A(N-phenyl-lnaphthylamine) and Neozone D (Nphenyl-Z-naphthylamine), areexamples of such amine antioxidants.

in light-colored or nonstaining neoprene-containing compositions, theuse of suitable nondiscoloring antioxidants is recommended. Thesubstituted or hindered phenols are the most widely used antioxidants ofthis class and generally give good aging properties combined withmaximum resistance to discoloration and staining. Examples of suchhindered phenols include Antioxidant 2246 which is 2,2-methylene-bis(4-methyl-6-t-butylphenol) and Antioxidant 425" which is 2,2-methylene-bis(4-ethyl-6-t-butylphenol). Another phenolic nonstainingantioxidant available commercially is Santowhite" powder as a 40 percentsolution in water.

Esters of unsaturated fatty acids have also been found to be useful toreduce the darkening of white and pastel-colored neoprene-containingcompositions. Principally, those oils of fatty acids having one or twodouble bonds are preferred. Examples of such oils include palm oil,predominantly palmittic acid, triglyceride; olive oil, predominantlyoleic acid triglyceride; and safflower oil, predominantly linoleic acidtriglyceride. Combinations of these esters with the nondiscoloringphenolic antioxidants have been found to be especially effective.

The incorporation of acid polymers into the compositions of thisinvention also provides a product having improved strength, andimpregnated fabrics having improved crease retention and flat stability.Acid polymers contemplated as being useful in this present invention areprepared from any of the polymerizable acids, i.e., those containingunsaturated groups. These polymers may be homopolymers of the acids orinterpolymers of the acids and other monomers. Such acids include, forexample, acrylic acid, maleic acid, methylacrylic acid and polymerizablephosphoric acids. Suitable monomers which may be copolymerized with theabove acids include esters of the above acids such as ethyl acrylate andmethyl methacrylate; alkyl fumarates and maleates; vinyl halides such asvinyl chloride; and other vinyl monomers such as styrene, acrylonitrile.

The acid polymers, as a general rule, are emulsion polymers containingvarying amounts of solids, normally in the range of about 25 to 60 or 70weight percent. Acrylic polymers of this type are readily availablecommercially (under the trade name Rhoplex), (under the trade namel-lycar), (under the trade name Ucon).

The compositions of the invention may also contain polymeric polyhydroxycompounds. These polyhydroxy compounds may be water-soluble orinsoluble. When incorporated into the compositions of the invention,they result in the formation of a fabric with improved flexibility andhandle. By polymeric polyhydroxy compound is meant a linear longchainpolymer having terminal hydroxyl groups including branched,polyfunctional, polymeric polyhydroxy compounds as set forth below.Among the suitable polymeric polyhydroxy compounds there are includedpolyether polyols such as polyalkylene ether glycols,polyalkylene-arylene etherthioether glycols and polyalkylene triols.Mixtures of these polyols may be used when desired.

The polyalkylene ether glycols may be represented by the formulal-lO(RO),,H, wherein R is an alkylene radical which need not be the samein each instance, and n is an integer. Examples of such glycols includepolyethylene ether glycol and polypropylene glycol. Polyalkylene ethertriols are obtained by reacting one or more alkylene oxides with one ormore lowmolecular weight aliphatic triols. The alkylene oxides mostcommonly used have molecular weights between about 44 and 250 and theseinclude for example, ethylene oxide, propylene oxide, butylene oxide,and 1,2-epoxyoctane.

Representative examples of the polyalkylene ether triols include:polypropylene ether triols (MW 700) made by reacting 608 parts of1,2-propylene oxide with 92 parts of glycerine;

polypropylene ether triols (MW 1535) made by reacting 1,401 parts of1,2-propylene oxide with 134 parts of trimethylol propane; andpolypropylene ether triol (MW 6000) made by reacting 5,866 parts of1,2-propylene oxide with 134 parts of 1,2,6-hexane triol.

Additional suitable polytriols include polyoxypropylene triols;polyoxybutylene triols; Niax triols LG56,LG42, and LGl l2; Triol TG400;and Actol 32-160.

Therrnosetting resins may also be included in the compositions of thisinvention in amounts up to about 10 percent by weight. Examples ofthermosetting resins which are useful include phenolic and aminoplastresins, such as the reaction products of phenol, cresol, xylenol, urea,melamine and substituted melamines with aldehydes such as formaldehyde,furfuraldehyde etc.

The term phenolic resins" is used herein in its conventional meaning andincludes the resinous materials made from phenol and aldehydes. Theseresins are also identified as phenoplasts. The most widely used phenolicresin is phenolformaldehyde although other suitable resins includephenolfurfural, p-tertiary-amyl phenol-formaldehyde and cresylicacid-formaldehyde.

The commercially important aminoplast resins are the urea formaldehydeand the melamine formaldehyde condensates. In general, these resins areformed by condensing an amine with an aldehyde such as by stirring onemole of urea with two moles of 37 percent formalin at 2530 C. inalkaline solution until the aldehyde is completely reacted. Theconditions for reacting melamine with aqueous formaldehyde are somewhatdifferent from the reactions of urea. Because of the low solubility ofmelamine in water, the reactions are usually conducted at temperaturesof 100 C. to bring the melamine into solution more readily. The aminogroups of melamine can each add two methylol groups, while in urea,apparently only one mole of formaldehyde adds to each amino group.Hexamethylol melamine is formed by heating melamine at C. with an excessof formaldehyde.

The alkyd resins are polyester resins obtained by reacting polyhydricalcohols such as glycols, glycerol, sorbitol, pentaerythritol etc., withpolybasic acids such as phthalic acid, maleic acid, adipic acid, azelaicacid and sebacic acid. These resins may be -modified with saturated andunsaturated monobasic acids, saturated and unsaturatedmonohydricalalcohols, etc. The oil modified alkyd resins are polyesterresins which have been modified with a drying and nondrying oil such ascoconut oil, castor oil, soybean oil, linseed oil, tung oil and theacids and glycerides derived therefrom. Examples of such alkyd resinsinclude coconut oil-modified glyceryl phthalate containing about 33percent by weight of fatty acids, and soybean oil-modified glycerylphthalate resins containing about 41 percent by weight of fatty acids.The alkyd resins are available commercially under a wide variety oftrade names from a variety of sources. Water-soluble alkyd resins areavailable under the trade name AROTAP.

Typical aldehyde generating compounds which can be incorporated into thecompositions of the invention include linear polymers, particularlythose of the general fonnula HO(Cl-1 O),,-H which depolymerize tomonomeric formaldehyde gas upon vaporization. In this class ofcompounds, there are included lower polyoxymethylene glycols, wherein nis from about 2 to 8; paraformaldehyde, wherein n ranges from about 6 toalpha-polyoxy methylenes, wherein n is greater than about 100; andbeta-polyoxy methylene wherein n is greater than about 100.

Polyoxy methylene glycol derivatives may also be utilized. Examplesinclude the polyoxymethylene diacetates and the lower polyoxymethylenedimethyl ethers. In general, higher temperatures, e.g., up to about 200C. are utilized to effect depolymerization of these derivatives.Formaldehyde acetate (formals) may also be utilized. Preferred formalsare produced by reaction of formaldehyde with alcohols of the formulaCHCH (OR) in the presence of an acid catalyst, wherein R is alkyl oraryl alkyl. These compounds hydrolize to formaldehyde and the parentalcohol. Preferred formals include methylal and 1,3-dioxolane.

Other suitable aldehyde generating compounds include the variousmethylol compounds, for example, methylol alkanolamine sulfites, such asN-methylol-ethanolamine suliite; methylol amides such as N-methylolformamide, N-methylol acetamide and N-methylol acrylamide; and aminessuch as trimethylolamine.

Also useful in the compositions of the invention are waterinsolublesilicone fluids such as SF-350, a dimethylsiloxane polymer. Othercommercially available dialkyl polysiloxanes are useful.

The surfactants and wetting agents may be either nonionic or anionic.Examples of nonionic wetting agents include alkyl aryl polyetheralcohols such as the ethylene oxide condensation products of octylphenolavailable under the trade name TRITON X-100 and the ethylene oxidecondensation products of nonyl phenol available under the trade nameAEROSOL OT. Examples of anionic wetting agents include metallic salts ofdisproportionated rosin acids and alkyl esters of sulphosuccinic acids.Specific examples of the latter wetting agents include the dihexyl esterof sodium sulphosuccinic acid available under the trade name AEROSOL NA,and the diamyl ester available under the trade name AEROSOL AY.

Although small amounts, for example, from about 0.1 to about 10 percentby weight of the surfactant wetting agent have been found to besufficient in the compositions of the inporated, for example, from about-10 percent.

The following examples illustrate the compositions useful in thisinvention.

Composition A Parts by Weight Neoprene 460 100 Bis phenol adduct ofmethylene bis(4-phenylisocyanate),

(40% in water) 50 Zinc oxide 7.5 Composition B Neoprene 460 50 Bisphenol adduct of Composition A l.5

Zinc oxide dispersion (50% in water) 7 Syn-Fae 905 (a nonionic wettingagent obtained by condensing 9.5 moles of ethylene oxide with a mole ofnonyl phenol) 1 Water 25 Composition C Neoprene 635 [00 Lead tetroxide7.5

Bis resorcinol adduct of hexamethylene diisocyanalelTrichlorochloroethylene I00 Composition D Neoprene Latex 635 (58%solids) 173 Zinc oxide dispersion (50% in water) l5 Neozone D; (NphenyI-Z-naphthylamine; 50% in water) 3 Nonic 2 l 8 (a nonionicsurfactant) 1 Composition E Neoprene Latex 750 (50% solids) 200 Zincoxide dispersion (50% in water) l5 Neozone D 3 Bis phenol adduct ofComposition A 50 Nonic 2l8 1 Composition F Neoprene Latex 750 (50%solids) 200 Zinc oxide dispersion (50% in water) l5NphenylQ-naphthylaminc (50% in water) 3 Bis phenol adduct of CompositionA 50 Rhoplex [5-358 (a self-crosslinlting acrylic emulsion Neozone A(N-phenyl-lnapthylamine; 50% in water) 3 Composition l Neoprene Latex750 (50% solids) Zinc oxide (50% in water) Santowhite powder Bis phenoladduct of Composition A Nonic 2l8 Composition .l

Composition 0, except that Latex 635 (50% solids) is used in lieu ofLatex 640 Hycar 267i (an acrylic emulsion; 50%) Polyethylene Glycol 600(a polyethylene glycol having a molecular weight of 600 WaterComposition K Composition G Hycar 2671 Ucon 50MB 2000 (a polyethyleneglycol prepared from a mixture of ethylene and propylene glycols) 5SynFac 905 Water Composition L Composition G (except that the Latex 750is replaced by Latex 635) Rhoplcx [3-358 Water Composition M CompositionG Trio] G 4000 (a water insoluble polypropylene glycol having amolecular weight of about 6000) Rhoplex E-358 Water Composition NComposition G H) Hycar 267l t5 Polyethylene Glycol 600 5 Aerosol OT(surfactant) 0.2 Water 69.8 Composition 0 Composition G 25 Hycar 2600 X92 (ac acrylic emulsion containing 50% solids) 20 Ucon 2000 5N-methylol-acetamide l0 Syntropol KB (wetting agent) I Water 64Composition P Same as Composition 0 except that the acetamide isreplaced by 10 parts of Rhonite R-l a dimethylol ethylene urea resin.Composition 0 Composition 6 25 Hycar 2671 20 Ucon 2000 5 Alkyd ResinM416 5 Melamine resin M387(a melamine-formaldehyde resin as an aqueoussolution) 0.5 Water 44.5

Composition R Composition 6 25 Hycar 2600 X 92 20 Alkyd resin M416 5Melamine resin M387 I Silicone SF 96-500 (a dimcthyl polysiloxanc fluid)l0 Water 39.5 Composition S Composition 0 20 Hycar 2600 X 92 I5Nmethylolacctamine 7 Alkyd Resin M4l6 5 Melamine Resin M387 1 SiliconeSF350 S Ucon 2000 10 Water 37 In preparing the compositions which aredispersions or emulsions, it is often desirable to prepare dispersionsof the separate ingredients which can then be mixed in the customarymanner. It has been found, for example, that it is difficult to preparea stable emulsion or dispersion containing the components when thecomponents are indiscriminately added to water. On the other hand,mixing of emulsions of the individual components is accomplishedreadily. Thus, for example, it is preferred in preparing dispersionssuch as composition G to prepare a zinc oxide dispersion containingabout 50 percent solids by stirring and mixing in a ball mill, 100 partsof zinc oxide in 35 parts of water, 30 parts of a l0 percent solution ofDexad 11, (a dispersing agent), 35 parts of a 10 percent solution ofammonium caseinate (a reacted casein), and 5 parts of a 10 percentsolution of sodium silicate. This mixture is milled for about 24 hoursto form a stable zinc oxide dispersion. The Santowhite powder (40percent solution) is likewise prepared in a ball mill by milling 100parts of the Santowhite powder in 80 parts of water, 30 parts of a 10percent solution of Dexad 1 l, 30 parts of a 10 percent solution ofammonium caseinate and 10 parts of alO percent solution of sodiumsilicate.

The bisphenol adduct dispersion (40 percent active ingredients) isprepared by the same procedure by milling 100 parts of the adduct with80 parts of water, 30 parts of A 10 percent solution of the Dexad ll, 30parts of a 10 percent solution of ammonium caseinate and l0 parts of a 5percent solution of Aerosol OP, a wetting agent.

After these separate emulsions are prepared, they are added to theNeoprene Latex 750 and Nonic 218 surfactant and mixed in theconventional manner.

In the preferred practice of this invention, the textile fabric isimpregnated with the compositions described above, either as solutions,dispersions or emulsion. The amount of solids contained in the solution,dispersion or emulsion preferably ranges from about 8 to 12 parts of theneoprene elastomer, from about 1 to 5 parts of the isocyanate and fromabout 0.2 to 1 part of the meta oxide, and the solids preferably shouldbe diluted to provide a liquid having a sufficiently low viscosity topennit the composition to impregnate the fabric. Generally, thesolution, dispersion or emulsion applied to the fabric will contain fromabout 40 to 50 percent by weight of solids.

The solutions, dispersions or emulsions are preferably padded on thefabric. Conventional padding or spraying equipment can be used for thispurpose. Generally, a wet pickup of from about 60-100 percent based onthe weight of the fabric is obtained providing for the incorporation ofabout 3050 percent of the chemical solids.

After impregnation of the fabrics as described above, the fabrics aredried and then either stored or processed further. At this point, theimpregnated fabrics have a propensity for subsequent durable settingwhich can be effected by heat curing in the dry state.

When the composition of the invention is prepared as an aqueous emulsionor dispersion and the diisocyanate is blocked such as by reaction with aphenol the fabric can be impregnated, dried and stored for a longerperiod of time since curing cannot be effected until the impregnatedmaterial is heated to a temperature suflicient to dissociate the blockedisocyanate. In most instances, the dissociation temperature issufficiently high to provide a presensitized fabric which is stable overa wide range of temperatures. For example, the phenol adduct utilized inComposition G dissociates at a temperature of about 320 F., andtherefore, the impregnated fabric must be heated at or above thistemperature to effect the cure and set the fabric.

It is this latter aspect of the invention that provides the mostdesirable properties. The utilization of compositions such asComposition G permits the preparation of presensitized fabrics which canbe cut, converted to garments and thereafter cured while beingmaintained in a preselected configuration to provide creases and pleatsas desired. These creases and pleats have been found to possess improvedwash and wear performance. That is, fabrics treated in this mannerexhibit improved crease and shape retention and reduced shrinking whenwashed in a commercial washing machine. Such improved properties areimparted by the present invention on virtually all types of fabricsranging from fabrics containing 100 percent natural fibers such ascotton or wool to fabrics composed exclusively of synthetic fibers, suchas polyesters and polyamides. Fabrics containing blends of these fibershave also been found to be improved by the compositions of theinvention. The compositions of the invention also have improved theperformance of laminated fabrics, such as for example fabrics composedof two or more layers of fabrics or an outer layer of a fabric and aninner layer of a foam such as a ureathane foam. impregnation of suchfabrics by the compositions of the invention does not effect the bondbetween the two layers, and can, therefore, be applied after laminationof the fabrics.

The following table illustrates the results obtained when a variety offabrics is treated in accordance with the process of the invention. Allthe fabrics listed in the table, except fabric 4 were impregnated withthe identified solutions to a wet pickup of 80 percent based on theweight of the fabric, dried, pressed on a Hoffman press utilizing acycle of 40 seconds steam, seconds bake and 5 seconds vacuum, andthereafter cured by heating to a temperature of 300 F. for a period ofminutes. The treatment of fabric 4 differs in that the wet pickup ofComposition K was 70 percent. The crease retention and flat dry resultsare based on a scale of from 1 to 5, 1 representing no crease retentionand 5 representing an excellent crease. As can be seen from the datacontained in the table, fabrics impregnated with the compositions of theinvention exhibit excellent crease retention and flat dry properties andimprove resistance to shrinkage.

TABLE Area Results shrinage (percent) Crease Flat dry after 5Comretenperformwashes at Fabric position tion 1 ance 2 105 (F.)

1. Wool/nylon tricot D 3. 4 4. 5 4. 3

laminate. 2. Wool/nylon tricot G 3. 2 4. 5 4. 4

laminate. 3. worsted wool K 3 3. 4 3 5. 3 4. White shirting (100% K I!4. 6 3 4. 6

cotton). 5. Same asl L 3.7 4.1

1 .AATGO Test N 0. 880 19641 (overhead); after five. 104 F. washes. 2AA'ICC Test No. 88 1964T (overhead); after five, 105 F. washes. 3 After10 washes.

That which is claimed is:

l. A process for preparing garments having improved permanent presscharacteristics which comprises a. treating a textile fabric with acomposition comprising i. a polychloroprene or a copolymer ofchloroprene with acrylonitrile,

an isocyanate compound selected from the group consisting ofpolyisocyanates, polyisothiocyanates, adducts of said isocyanates withcompounds possessing only one group containing a reactive hydrogen atomand mixtures of said isocyanates or adducts of isocyanates, and

iii. a metal oxide selected from the group consisting of the oxides ofthe group II metals, iron, lead and titanium;

b. converting the treated fabric into a garment;

c. maintaining the garment in a desired configuration; and

d. subjecting the garment to a temperature sufiicient to cure thetreated fabric.

2. The process of claim 1 wherein the metal oxide is zinc oxide.

3. The process of claim 1 wherein the textile fabric is treated with anaqueous dispersion of the composition, and the isocyanate compound is anisocyanate adduct.

4. The process of claim 1 wherein the composition comprises from about 8to 12 parts of polychloroprene, from about i to 5 parts of theisocyanate compound and from about 0.2 to 1 part of the metal oxide.

5. The process of claim 4 wherein the isocyanate is an alkylenediisocyanate.

6. The process of claim 1 wherein the textile fabric is a fabriccontaining at least some natural fibers.

7. A process for preparing garments having improved permanent presscharacteristics which comprises a. impregnating a textile fabric with acomposition comprisi. a chloroprene polymer or a copolymer ofchloroprene with acrylonitrile,

ii. an adduct of a polyisocyanate with a compound having only one groupcontaining a reactive hydrogen atom, and

iii. a small amount of zinc oxide, magnesium oxide or calcium oxide;

b. drying the treated fabric;

c. converting the treated fabric into a garment;

d. maintaining the garment in a desired configuration; and

e. subjecting the garment to a temperature sufficient to cure thetreated fabric.

8. The process of claim 7 wherein the polyisocyanate adduct is an aryldiisocyanate adduct.

9. The process of claim 7 wherein the metal oxide is zinc oxide.

10. The process of claim 7 wherein the composition also contains anantioxidant and an acrylic polymer.

2. The process of claim 1 wherein the metal oxide is zinc oxide.
 3. The process of claim 1 wherein the textile fabric is treated with an aqueous dispersion of the composition, and the isocyanate compound is an isocyanate adduct.
 4. The process of claim 1 wherein the composition comprises from about 8 to 12 parts of polychloroprene, from about 1 to 5 parts of the isocyanate compound and from about 0.2 to 1 part of the metal oxide.
 5. The process of claim 4 wherein the isocyanate is an alkylene diisocyanate.
 6. The process of claim 1 wherein the textile fabric is a fabric containing at least some natural fibers.
 7. A process for preparing garments having improved permanent press characteristics which comprises a. impregnating a textile fabric with a composition comprising i. a chloroprene polymer or a copolymer of chloroprene with acrylonitrile, ii. an adduct of a polyisocyanate with a compound having only one group containing a reactive hydrogen atom, and iii. a small amount of zinc oxide, magnesium oxide or calcium oxide; b. drying the treated fabric; c. converting the treated fabric into a garment; d. maintaining the garment in a desired configuration; and e. subjecting the garment to a temperature sufficient to cure the treated fabric.
 8. The process of claim 7 wherein the polyisocyanate adduct is an aryl diisocyanate adduct.
 9. The process of claim 7 wherein the metal oxide is zinc oxide.
 10. The process of claim 7 wherein the composition also contains an antioxidant and an acrylic polymer. 